1190 Kadu et al.
Asian J. Chem.
10 mL) and then filtered to afford the crude product, which
was used further by water washing and drying properly without
purification to afford the desired product 4.
IR (KBr, νmax, cm–1): 3302, 2371, 1592, 1254; 1H NMR (400
MHz, DMSO-d6): δ = 7.81 (s, 2H, NH2), 7.57 (q, J = 7.91 Hz,
4H, ArH), 7.21 (t, J = 7.78 Hz, 2H, ArH), 7.06 (d, J = 7.96,
2H, ArH), 6.75 (t, J = 7.27 Hz, 1H, ArH) ppm; 13C NMR (100
MHz, CDCl3): δ 145.12, 135.12, 134.12, 131.51, 129.09,
127.39, 120.61, 118.95, 112.03 ppm; Anal. calcd. (found) %
for C16H11N4Br: C, 56.66 (56.64); H, 3.27 (3.28); Br, 23.56
(23.55); N, 16.52 (16.54).
5-Amino-1-phenyl-3-phenyl-1H-pyrazole-4-carbo-
nitrile (4a): Pale yellow solid, yield 93 %; m.p.: 159-160 °C;
IR (KBr, νmax, cm–1): 3293, 2363, 1601, 1256; 1H NMR (400
MHz, CDCl3): δ = 7.70 (m, 2H, ArH), 7.68 (s, 2H, NH2), 7.40
(m, 2H, ArH), 7.33 (m, 3H, ArH), 7.29 (m, 2H, ArH), 6.91
(m, 1H, ArH) ppm; 13C NMR (100 MHz, CDCl3): δ 144.68,
137.33, 135.33, 129.79, 129.33, 129.03, 128.63, 128.44, 128.37,
126.21, 120.13, 112.79 ppm;Anal. calcd. (found) % for C16H12N4:
C, 73.83 (73.84); H, 4.65 (4.63); N, 21.52 (21.54).
5-Amino-3-(4-nitrophenyl)-1-phenyl-1H-pyrazole-4-
carbonitrile (4g): Red solid, yield 95 %; m.p.: 164-166 °C;
IR (KBr, νmax, cm–1): 3465, 3355, 3105, 2354, 1610, 1417,
1
1456, 1345, 1256, 1133, 1108, 1094; H NMR (400 MHz,
5-Amino-1-phenyl-3-p-tolyl-1H-pyrazole-4-carbo-
nitrile (4b): Pink powder solid, yield 90 %; m.p.: 117-119
°C; IR (KBr, νmax, cm–1): 3482, 3319, 3095, 2925, 2359, 1598,
1415, 1257, 1127, 1113, 1096; 1H NMR (400 MHz, CDCl3):
δ 2.41 (s, 3H), 6.91 (dd, J = 3.5 Hz and J = 7.3 Hz, 1H), 7.15
(d, J = 7.76 Hz, 2H), 7.22 (d, J = 7.9 Hz, 2H), 7.29–7.33 (m,
CDCl3): δ = 8.25 (d, J = 7.6 Hz, 2H) 8.03 (s, 1H), 7.74-7.77
(m, 3H), 7.20–7.34 (m, 2H), 7.18 (d, J = 7.6 Hz, 2H), 6.96 (s,
1H) ppm; 13C NMR (100 MHz, CDCl3): δ 156.53, 149.56,
145.26, 137.73, 135.32, 131.72, 130.93, 129.90, 122.78, 122.15,
123.47, 113.43, 112.36 ppm; Anal. calcd. (found) % for
C16H11N5O2: C, 62.95 (62.96); H, 3.63 (3.61); N, 22.94 (22.96);
O, 10.48 (10.47).
13
2H), 7.59 (d, J = 7.9 Hz, 2H), 7.70 (s, 2H) ppm; C NMR
(100 MHz, CDCl3): δ 153.20, 148.82, 145.20, 138.97, 138.14,
132.95, 129.77, 129.71, 126.62, 120.44, 113.22, 104.65, 21.90
ppm; Anal. calcd. (found) % for C17H14N4: C, 74.43 (74.45);
H, 5.14 (5.13); N, 20.42 (20.43).
5-Amino-3-(2-chlorophenyl)-1-phenyl-1H-pyrazole-4-
carbonitrile (4h): Yellow solid, yield 90 %; m.p.: 139-141
°C; IR (KBr, νmax, cm–1): 3475, 3425, 3150, 2520, 2335, 1660,
1575, 765, 720; 1H NMR (400 MHz, CDCl3): δ = 7.61 (s, 2H)
7.58 (d, J = 8.4 Hz, 2H), 7.35 (d, J = 8.4 Hz, 2H), 7.28–7.32
(m, 2H), 7.15 (d, J = 7.6 Hz, 2H), 6.94 (t, J = 7.6 Hz, 1H)
ppm; 13C NMR (100 MHz, CDCl3): δ 154.82, 144.87, 144.43,
139.44, 138.52, 137.90, 129.41, 128.54, 127.04, 119.34, 117.25,
112.84, 114.04, 99.48 ppm; Anal. calcd. (found) % for
C16H11N4Cl: C, 65.20 (65.22); H, 3.76 (3.75); Cl, 12.03 (12.02);
N, 19.01 (19.02).
5-Amino-3-(4-cyanophenyl)-1-phenyl-1H-pyrazole-4-
carbonitrile (4i):Yellow solid, yield 94 %; m.p. 158-160 °C;
IR (KBr, νmax, cm–1): 3434, 3316, 3275, 2353, 2229, 1583,
1472, 1265, 1155, 1127, 1096; 1H NMR (400 MHz, CDCl3):
δ 10.72 (s, 1H, ArH), 7.85 (s, 1H, NH), 7.77-7.81 (m, 4H,
ArH), 7.24 (t, J = 7.2 Hz, 2H, ArH), 7.13 (d, J = 7.6 Hz, 2H,
ArH), 6.82 (t, J = 7.2 Hz, 1H,ArH) ppm; 13C NMR (100 MHz,
CDCl3): δ 152.34, 146.19, 137.83, 135.75, 129.70, 128.15,
127.09, 126.74, 120.56, 117.92, 115.61, 113.25, 112.82 ppm;
Anal. calcd. (found) % for C17H11N5: C, 71.57 (71.58); H, 3.89
(3.88); N, 24.55 (24.57).
5-Amino-1-(3-chlorophenyl)-3-phenyl-1H-pyrazole-4-
carbonitrile (4j): Pale yellow solid, yield 92 %; m.p.: 172-
175 °C; 1H NMR (400 MHz, CDCl3): δ = 7.72-7.68 (m, 1H,
ArH), 7.64 (s, 2H, NH2), 7.43-7.35 (m, 3H, ArH), 7.22-7.20
(m, 2H, ArH), 7.18 (s, 1H, ArH), 6.93 (dd, J = 8.4 & 1.6 Hz,
1H, ArH), 6.86 (dd, J = 8.0 & 1.2 Hz, 1H, ArH) ppm; 13C
NMR (100 MHz, CDCl3): δ 145.77, 138.36, 135.20, 134.88,
130.25, 128.81, 128.67, 126.37, 119.96, 112.80, 110.89 ppm;
Anal. calcd. (found) % for C16H11N4Cl: C, 65.20 (65.22); H,
3.76 (3.78); Cl, 12.03 (12.05); N, 19.01(19.03).
5-amino-3-(5-bromo-2-hydroxyphenyl)-1-(4-bromo-
phenyl)-1H-pyrazole-4-carbonitrile (4k):Yellow solid, yield
87 %; m.p.: 180-182 °C; 1H NMR (400 MHz, CDCl3): δ 9.23
(s, 1H, OH, Ar-OH), 7.83 (s, 1H, ArH), 7.23-7.34 (m, 5H),
6.83 (d, 3H, ArH) ppm; 13C NMR (100 MHz, CDCl3): δ 155.9,
142.71, 139.59, 132.17, 132.10, 131.22, 120.64, 118.31, 113.98,
112.13, 111.0 ppm;Anal. calcd. (found) % for C16H10N4OBr2:
5-Amino-1-phenyl-3-(4-methoxyphenyl)-1H-pyrazole-
4-carbonitrile (4c): Cream coloured solid, yield 91 %; m.p.:
106-108 °C; IR (KBr, νmax, cm–1): 3313, 2363, 1595, 1244; 1H
NMR (400 MHz, DMSO-d6): δ = 7.81 (s, 2H, NH2), 7.57 (d, J
= 8.76 Hz, 2H, ArH), 7.19 (t, J = 7.84, 2H, ArH), 7.03 (d, J =
8.00 Hz, 2H, ArH), 6.95 (d, J = 8.76 Hz, 2H, ArH), 6.71 (t, J
= 7.22 Hz, 1H, ArH), 3.77 (s, 3H, OCH3) ppm; 13C NMR (100
MHz, CDCl3): δ 159.26, 145.53, 136.53, 133.34, 129.01,
128.46, 126.98, 118.28, 114.13, 111.76, 55.13 ppm; Anal.
calcd. (found) % for C17H14N4O: C, 70.33 (70.35); H, 4.86
(4.84); N, 19.30 (19.31); O, 5.51 (5.50).
5-Amino-1-phenyl-3-(4-hydroxyphenyl)-1H-pyrazole-
4-carbonitrile (4d): Brown solid, yield 89 %; m.p.: 210-212
1
°C; IR (KBr, νmax, cm–1): 3398, 2181, 1688, 1257; H NMR
(400 MHz, DMSO-d6): δ = 9.61 (s, 1H, OH), 7.77 (s, 2H,
NH2), 7.46 (d, J = 8.56 Hz, 2H, ArH), 7.18 (t, J = 7.84 Hz, 2H,
ArH), 7.01 (d, J = 7.72, 2H,ArH), 6.78 (d, J = 8.56, 2H, ArH),
6.69 (t, J = 7.24 Hz, 1H, ArH) ppm; 13C NMR (100 MHz,
CDCl3): δ 157.64, 145.65, 137.08, 127.12, 126.86, 118.09,
115.50, 112.04, 111.68 ppm; Anal. calcd. (found) % for
C16H12N4O: C, 69.55 (69.56); H, 4.38 (4.39); N, 20.28 (20.27);
O, 5.79 (5.78).
5-Amino-1-(4-chlorophenyl)-3-phenyl-1H-pyrazole-4-
carbonitrile (4e): Pink solid, yield 92 %, m.p.: 133-135 °C;
IR (KBr, νmax, cm–1): 3420, 3322, 3095, 2365, 1598, 1487,
1267, 1134, 1096; 1H NMR (400 MHz, CDCl3): δ = 7.70 (s,
1H), 7.66 (d, J = 7.6 Hz, 2H), 7.56 (s, 1H), 7.42 (t, J = 7.6 Hz,
2H), 7.33–7.36 (m, 1H), 7.25 (d, J = 8.4 Hz, 2H), 7.06 (d, J =
8.8 Hz, 2H) ppm; 13C NMR (100 MHz, CDCl3): δ 155.92,
143.67, 138.37, 135.41, 132.28, 129.52, 129.09, 129.02, 126.60,
125.08, 114.22, 112.05ppm;Anal. calcd. (found)%forC16H11ClN4:
C, 65.20 (65.22); H, 3.76 (3.75); Cl, 12.03 (12.02); N, 19.01
(19.03).
5-Amino-1-phenyl-3-(4-bromophenyl)-1H-pyrazole-4-
carbonitrile (4f): Pink solid, yield 93 %; m.p.: 165-167 °C;